CN102417432A - Method for preparing 1,3-butadiene through catalytic dehydrogenation of butane - Google Patents
Method for preparing 1,3-butadiene through catalytic dehydrogenation of butane Download PDFInfo
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- CN102417432A CN102417432A CN2011104233990A CN201110423399A CN102417432A CN 102417432 A CN102417432 A CN 102417432A CN 2011104233990 A CN2011104233990 A CN 2011104233990A CN 201110423399 A CN201110423399 A CN 201110423399A CN 102417432 A CN102417432 A CN 102417432A
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- butadiene
- butane
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- butylene
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Abstract
The invention discloses a method for preparing 1,3-butadiene through catalytic dehydrogenation of butane. Two products, namely butene and 1,3-butadiene are obtained in the dehydrogenation process of the butane; and the reaction is also strong endothermic reaction and is carried out at the temperature of more than 500 DEG C under lower partial pressure of the butane in the presence of a catalyst. The reaction temperature of an industrial device for dehydrogenating the butane is about 600 DEG C; and the lower conversion per pass is maintained by shortening the contact time.
Description
Technical field
The present invention relates to a kind of alkanes Chemicals, particularly a kind of method that adopts catalytic dehydrogenation of butanes to prepare 1,3-butadiene is suitable for the synthetic 1,3-butadiene of chemical industry
Background technology
C-C singly-bound internal rotation in
butadiene molecule is divided into cis and transconfiguration.The transconfiguration molecule is stable.These article are prone to liquefaction for having the colourless gas of faint aromatic odour.Fusing point-108.9 ℃, boiling point-4.41 ℃, specific density 0.6211 (20/4 ℃), zero pour-108.91 ℃, flash-point＜-6 ℃, specific refractory power 1.4292 (25 ℃), 152 ℃ of critical temperatures, emergent pressure 4326.58kPa, critical density 0.245g/cm3.Form explosive mixture, limits of explosion 2%-11.5% (vol) with air.Be dissolved in pure and mild ether, also dissolve in acetone, benzene, ethylene dichloride, amyl acetate-n and furfural, the CAA solution.Water insoluble.Easy polymerization in the presence of oxygen.Can add used as stabilizers such as a small amount of (below 1%) tert-butyl catechol, Resorcinol, mixture cresol, diarylamine based compound during storage.Purposes: divinyl is to produce elastomeric main raw material, for example, and styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, paracril, X 050 or the like.Along with the development of styrene plastic(s), utilize vinylbenzene and butadiene copolymer, the production various uses is resin (like ABS resin, SBS resin, BS resin, MBS resin) widely, makes divinyl in production of resins, occupy critical role gradually.In addition, divinyl still is used to produce ENB (ethylene-propylene rubber(EPR) the 3rd monomer), 1,4-butyleneglycol (engineering plastics), adiponitrile (nylon 66 monomers), tetramethylene sulfone, anthraquinone, THF or the like.Thereby also be important basic chemical industry raw material.Divinyl also has a lot of use in fine chemicals production.With the divinyl is the fine chemicals that raw material is produced.Mainly contain the following aspects.(1) have a liking for bifunctional vinyl compound generation Diels-Alder reaction with electron deficiency, make anthraquinone, its verivate is important dyestuff intermediate, sterilant and sterilant.(2) with MALEIC ANHYDRIDE (abbreviation cis-butenedioic anhydride) reaction, so condensation, make THPA, can make polyester resin, curing agent for epoxy resin and softening agent.THPA can get BTCA again through nitric acid oxidation, is the raw material of making water soluble paint.Same THPA hydrogenation makes hexahydrophthalic acid anhydride, can be used as curing agent for epoxy resin.(3) with the sulfurous gas effect, generate cyclobufene sultone, be mixed with aqueous solution hydrogenation in the presence of skeletal nickel catalyst then, make tetramethylene sulfone, be the selective solvent that aromatic hydrocarbons extraction is used.The mixture of tetramethylene sulfone and HSDB 338 can use decarbonation gas to use.(4) the line style telomerization of divinyl is very useful in industry.Obtain eight carbon normal olefines after the line style dimerization, promptly get nonyl alcohol through hydroformylation, hydrogenation again, important use is all being arranged aspect synthetic perfume, tensio-active agent, the oil dope.Make catalyzer with cobalt complex, its dimerization, trimerization, the tetramer all are the raw materials of synthetic higher alcohols and megacyclic musk.
prior art is to adopt ethylene unit by-product C4 extracting (sub product of aliphatic hydrocarbon when ethene is produced in 900 ° of steam crackinges of generation more than the C with other alkene).The divinyl that generates can extract through acetonitrile or N isopolarity aprotic solvent, and distillation is purified.This method mainly must be produced with the ethene coproduction, and it is very big influenced by major product ethylene production amount and other products, can not control turnout
Summary of the invention
problem to be solved by this invention is, overcomes the deficiency of prior art, and a kind of method that adopts catalytic dehydrogenation of butanes to produce 1,3-butadiene is provided.The butane dehydrogenation process obtains butylene and two kinds of products of 1,3-butadiene, and reaction also is a strong endothermic reaction, must and have in the presence of the catalyzer in high temperature more than 500 ℃, lower butane dividing potential drop to carry out.The temperature of reaction of butane dehydrogenation full scale plant keeps lower per pass conversion to produce the 1.3-divinyl through shortening duration of contact about 600 ℃.
For realizing above-mentioned purpose, the invention discloses following technology contents:
(1) in a reactor drum, adopt the chromic oxide of catalyzer 18%-20% to be immersed on the aluminum oxide, then butane dehydrogenation is become butylene, butylene dehydrogenation generates 1,3-butadiene; Temperature of reaction is 550-650 ℃, and pressure is 0.0946-0.379kPa (absolute pressure), and air speed is 1-3h
-1
(volume); Wherein the ratio of weight and number of butane and catalyzer is 1000:1
(2) are come out in quench tower directly and circulation cooling oil contact cooling by reactor drum, deliver to absorption-stable system through compressing again; The mixture of isolated butylene and 1,3-butadiene is isolated the polymerization-grade 1,3-butadiene through acetonitrile (ratio of weight and number of consumption is 1:1) extractive distillation.
Preparing method of the present invention, wherein the Preparation of catalysts method is following:
preparation method of the present invention, wherein said in a reactor drum, refer to: what reactor drum carried out is reaction and regeneration operate alternately; Wherein the time of regenerative operation is 5-15min, and catalyst life was generally 18-24 month.
present method is used as the raw material butane purity of dehydrogenation system 1,3-butadiene must be more than 95%.The butane dehydrogenation process obtains butylene and two kinds of products of 1,3-butadiene, and reaction also is a strong endothermic reaction, goes up feasible transformation efficiency and selectivity in order to obtain industry, and reaction must and have in the presence of the catalyzer in high temperature more than 500 ℃, lower butane dividing potential drop to be carried out.Relevant temperature of reaction and pressure are to having listed the data of typical equilibrium conversion in the data of the equilibrium relationship between 1,3-butadiene and three butylene isomers such as the following table.The best temperature of reaction of butane dehydrogenation full scale plant takes place with side reaction in order to reduce the knot charcoal about 600 ℃, keeps lower per pass conversion duration of contact through shortening.
Butane dehydrogenation is a 1-butylene molecular balance transformation efficiency
Butane dehydrogenation thermodynamic change rate
butane dehydrogenation becomes butylene, and butylene dehydrogenation generates the 1,3-butadiene two-step reaction and in a reactor drum, carries out simultaneously.The process catalyst system therefor is immersed on the aluminum oxide by the chromic oxide of 18%-20% and forms.Temperature of reaction is 550-650 ℃, and pressure is 0.0946-0.379kPa (absolute pressure), and air speed is 1-3h
-1
(volume).Because catalyzer has greater activity, process need not water vapor dilution raw material, and reactive deposition is at the normal pressure overfire air burning-off commonly used during at catalyst regeneration of the knot charcoal on the catalyzer, and what therefore a bank of reactor was carried out is reaction and regeneration operate alternately.Reaction times is generally 5-15min, catalyst life was generally 18-24 month, also has to surpass 4 years.Butane dehydrogenation generates the mixture of butylene and 1,3-butadiene, is come out in quench tower directly and circulation cooling oil contact cooling by reactor drum, and warp compresses and delivers to absorption-stable system again.The mixture of isolated butylene and 1,3-butadiene goes out the polymerization-grade 1,3-butadiene through acetonitrile or furfural extraction fractionation by distillation.Process butane per pass conversion has only 28%-30%, and selectivity is 55%-65%, and total recovery is 62%-63%, and the material balance of process sees the following form:
The material balance of process
The 1,3-butadiene of the present invention's preparation has following character:
1,3-butadiene: colourless gas is prone to liquefaction.Fusing point-108.9 ℃, boiling point-4.41 ℃, specific density 0.6211 (20/4 ℃), zero pour-108.91 ℃, flash-point＜-6 ℃, specific refractory power 1.4292 (25 ℃), 152 ℃ of critical temperatures, emergent pressure 4326.58kPa, critical density 0.245g/cm3.The present invention adopts method that catalytic dehydrogenation of butanes prepares 1,3-butadiene compared with prior art, has the following advantages:
(1) present method can continous-stable the preparation 1,3-butadiene, solved original batch fractionating can not stably manufactured drawback.
(2) integrated continuous dosing production can better utilised cold and heat, makes production cost lower.
Steady quality behind
(3) continuous production can large-scale industrial production.
Description of drawings:
Fig. 1 is one step of a butane dehydrogenating technology flow process; 1-airheater wherein; The 2-feed heater; The 3-reactor drum; The 4-stabilizer tower; The 5-stripping tower; The 6-absorption tower; The 7-compressor; The 8-quench tower; The 9-waste heat boiler.
Embodiment:
The present invention is explained below in conjunction with embodiment in
; The scheme of embodiment described here; Do not limit the present invention; One of skill in the art can make improvements and change according to spirit of the present invention, and described these improvement and variation all should be regarded as within the scope of the invention, and scope of the present invention and essence are limited claim.
Embodiment 1
Adopt catalytic dehydrogenation of butanes to prepare the method for 1,3-butadiene:
(1) adopts the chromic oxide of catalyzer 18% to be immersed on the aluminum oxide in a reactor drum, then butane (98%) is dehydrogenated to butylene, and butylene dehydrogenation generates 1,3-butadiene; Temperature of reaction is 550 ℃, and pressure is 0.0946kPa (absolute pressure), and air speed is 1h-1 (volume); Wherein the ratio of weight and number of butane and catalyzer is 1:0.5.
(2) are come out in quench tower directly and circulation cooling oil contact cooling by reactor drum, deliver to absorption-stable system through compressing again.The mixture of isolated butylene and 1,3-butadiene goes out the polymerization-grade 1,3-butadiene through acetonitrile or furfural extraction fractionation by distillation.Process butane per pass conversion has only 30%, and selectivity is 65%, and total recovery is 63%,
Embodiment 2
(1) adopts the chromic oxide of catalyzer 20% to be immersed on the aluminum oxide in a reactor drum, then butane dehydrogenation is become butylene, and butylene dehydrogenation generates 1,3-butadiene; Temperature of reaction is 650 ℃, and pressure is 0.379kPa (absolute pressure), and air speed is 3h-1 (volume); Wherein the ratio of weight and number of butane and catalyzer is 1:0.8.
(2) come out in quench tower directly and circulation cooling oil contact cooling by reactor drum, deliver to absorption-stable system through compressing again; The mixture of isolated butylene and 1,3-butadiene is isolated the polymerization-grade 1,3-butadiene through acetonitrile (ratio of weight and number of consumption is 1:1) extractive distillation
Claims (3)
1. method that adopts catalytic dehydrogenation of butanes to prepare 1,3-butadiene is characterized in that:
(1) in a reactor drum, adopt the chromic oxide of catalyzer 18%-20% to be immersed on the aluminum oxide, then butane dehydrogenation is become butylene, butylene dehydrogenation generates 1,3-butadiene; Temperature of reaction is 550-650 ℃, and pressure is 0.0946-0.379kPa (absolute pressure), and air speed is 1-3h-1 (volume); Wherein the ratio of weight and number of butane and catalyzer is 1000:1
(2) come out in quench tower directly and circulation cooling oil contact cooling by reactor drum, deliver to absorption-stable system through compressing again; The mixture of isolated butylene and 1,3-butadiene is isolated the polymerization-grade 1,3-butadiene through acetonitrile (ratio of weight and number of consumption is 1:1) extractive distillation.
2. the described preparation method of claim 1 is wherein said in a reactor drum, refers to: what reactor drum carried out is reaction and regeneration operate alternately; Wherein the time of regenerative operation is 5-15min, and catalyst life was generally 18-24 month.
3. the described preparation method of claim 1, wherein said butane purity is more than 95%.
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| CN2011104233990A CN102417432A (en) | 2011-12-16 | 2011-12-16 | Method for preparing 1,3-butadiene through catalytic dehydrogenation of butane |
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| CN2011104233990A CN102417432A (en) | 2011-12-16 | 2011-12-16 | Method for preparing 1,3-butadiene through catalytic dehydrogenation of butane |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105683137A (en) * | 2013-11-12 | 2016-06-15 | 陶氏环球技术有限责任公司 | Catalytic dehydrogenation process |
| US10391477B2 (en) | 2016-09-30 | 2019-08-27 | Uchicago Argonne, Llc | Multimetallic catalysts |
| US10828621B2 (en) | 2017-08-28 | 2020-11-10 | Uchicago Argonne, Llc | Supported multimetallic catalysts for oxidative dehydrogenation of alkanes |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4312780A (en) * | 1980-09-15 | 1982-01-26 | Air Products And Chemicals, Inc. | Reactivation of spent chromia-alumina catalyst by zinc oxide doping |
| CN1668556A (en) * | 2002-07-12 | 2005-09-14 | 巴斯福股份公司 | Method for the production of butadiene from n-butane |
| CN1902150A (en) * | 2003-12-30 | 2007-01-24 | 巴斯福股份公司 | Method for the production of butadiene |
-
2011
- 2011-12-16 CN CN2011104233990A patent/CN102417432A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4312780A (en) * | 1980-09-15 | 1982-01-26 | Air Products And Chemicals, Inc. | Reactivation of spent chromia-alumina catalyst by zinc oxide doping |
| CN1668556A (en) * | 2002-07-12 | 2005-09-14 | 巴斯福股份公司 | Method for the production of butadiene from n-butane |
| CN1902150A (en) * | 2003-12-30 | 2007-01-24 | 巴斯福股份公司 | Method for the production of butadiene |
Non-Patent Citations (2)
| Title |
|---|
| 无: "丁二烯的生产", 《合成橡胶工业》, no. 1, 31 December 1978 (1978-12-31) * |
| 胥月兵等: "CrOx／Si02催化剂对正丁烷催化脱氢反应的催化性能", 《石油炼制与化工》, vol. 39, no. 7, 31 July 2008 (2008-07-31), pages 41 - 46 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105683137A (en) * | 2013-11-12 | 2016-06-15 | 陶氏环球技术有限责任公司 | Catalytic dehydrogenation process |
| US10391477B2 (en) | 2016-09-30 | 2019-08-27 | Uchicago Argonne, Llc | Multimetallic catalysts |
| US10828621B2 (en) | 2017-08-28 | 2020-11-10 | Uchicago Argonne, Llc | Supported multimetallic catalysts for oxidative dehydrogenation of alkanes |
| US11738331B2 (en) | 2017-08-28 | 2023-08-29 | Uchicago Argonne, Llc | Supported multimetallic catalysts for oxidative dehydrogenation of alkanes |
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Application publication date: 20120418 |